Influence of temporally variable groundwater flow conditions on point measurements and contaminant mass flux estimations

Monitoring of contaminant concentrations, e.g., for the estimation of mass discharge or contaminant degradation rates, often is based on point measurements at observation wells. In addition to the problem, that point measurements may not be spatially representative, a further complication may arise due to the temporal dynamics of groundwater flow, which may cause a concentration measurement to be not temporally representative. This paper presents results from a numerical modeling study focusing on temporal variations of the groundwater flow direction. “Measurements” are obtained from point information representing observation wells installed along control planes using different well frequencies and configurations. Results of the scenario simulations show that temporally variable flow conditions can lead to significant temporal fluctuations of the concentration and thus are a substantial source of uncertainty for point measurements. Temporal variation of point concentration measurements may be as high as the average concentration determined, especially near the plume fringe, even when assuming a homogeneous distribution of the hydraulic conductivity. If a heterogeneous hydraulic conductivity field is present, the concentration variability due to a fluctuating groundwater flow direction varies significantly within the control plane and between the different realizations. Determination of contaminant mass fluxes is also influenced by the temporal variability of the concentration measurement, especially for large spacings of the observation wells. Passive dosimeter sampling is found to be appropriate for evaluating the stationarity of contaminant plumes as well as for estimating average concentrations over time when the plume has fully developed. Representative sampling has to be performed over several periods of groundwater flow fluctuation. For the determination of mass fluxes at heterogeneous sites, however, local fluxes, which may vary considerably along a control plane, have to be accounted for. Here, dosimeter sampling in combination with time integrated local water flux measurements can improve mass flux estimates under dynamic flow conditions.     

Model-based prediction of long-term leaching of contaminants from secondary materials in road constructions and noise protection dams

In this study, contaminant leaching from three different secondary materials (demolition waste, municipal solid waste incineration ash, and blast furnace slag) to groundwater is assessed by numerical modeling. Reactive transport simulations for a noise protection dam and a road dam (a typical German autobahn), in which secondary materials are reused as base layers, were performed to predict the breakthrough of a conservative tracer (i.e., a salt) and sorbing contaminants (e.g., PAHs like naphthalene and phenanthrene or heavy metals) at the groundwater table. The dam constructions have a composite architecture with soil covers in inclined layers and distinct contrasts in the unsaturated hydraulic properties of the used materials. Capillary barrier effects result in strong spatial variabilities of flow and transport velocities. Contaminant breakthrough curves at the groundwater table show significant tailing due to slow sorption kinetics and a wide distribution of travel times. While conservative tracer breakthrough depends primarily on subsoil hydraulic properties, equilibrium distribution coefficients and sorption kinetics represent additional controlling factors for contaminant spreading. Hence, the three secondary materials show pronounced differences in the temporal development of leached contaminant concentrations with consequences for breakthrough times and peak concentrations at the groundwater table. Significant concentration reductions due to dispersion occur only if the source concentrations decrease significantly prior to the arrival of the contaminant at the groundwater table. Biodegradation causes significant reduction of breakthrough concentrations only if flow velocities are low.     

Vertical profile of PCDD/Fs, dioxin-like PCBs, other PCBs, PAHs, chlorobenzenes, DDX, HCHs, organotin compounds and chlorinated ethers in dated sediment/soil cores from flood-plains of the river Elbe, Germany

Concentrations of polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) and other organic micropollutants were determined in dated sediment/soil cores collected from the flood-plain of the river Elbe near Pevestorf (PT), approximately 125 km upstream of Hamburg, and Heuckenlock (HL) in southeast of Hamburg. Concentrations of PCDD/Fs peaked sharply at PT in the 1950s and at HL at the end of the 1940s. Cluster analyses provide evidence that the region of Bitterfeld-Wolfen (about 350-400 km upstream of Hamburg) could be the source of the PCDD/F contamination existing in the cores PT and HL since the 1940s. Obviously it is caused by sediments of the river Elbe of a similar composition. Whereas the PCDD/Fs, HCHs (hexacyclohexane isomers), DDX (DDT, DDD, DDE), and tetrachlorinated ethers in PT and HL presumably originated predominantly from the Bitterfeld-Wolfen region, organotin compounds in HL and dichlorinated haloethers in HL during the 1940s and 1950s can probably largely be attributed to emissions from the Hamburg region. Although they are separated by a large distance, in both sediment cores PT and HL concentrations and composition patterns of most organic micropollutants analyzed widely match. Inductively it can be concluded that similar contaminations will be found in many of the river bank soils between the Bitterfeld-Wolfen region and Hamburg. Excavation of top soils may uncover highly contaminated materials. Since the dated sediment cores show the variation in contaminants in the Elbe sediments over a defined time period, it is possible to make an approximate assessment of the actual degree of contamination to be expected in areas where in previous decades contaminated dredged sediments from the Elbe and from the Port of Hamburg have been deposited on land and used for building plots or for agricultural purposes.     

The influence of EDDS and EDTA on the uptake of heavy metals of Cd and Cu from soil with tobacco Nicotiana tabacum

Phytoextraction, the use of plants to extract contaminants from soils and groundwater, is a promising approach for cleaning up soils contaminated with heavy metals. In order to enhance phytoextraction the use of chelating agents has been proposed. This study aims to assess whether ethylene diamine disuccinate (EDDS), a biodegradable chelator, can be used for enhanced phytoextraction purposed, as an alternative to ethylene diamine tetraacetate (EDTA). EDDS revealed a higher toxicity to tobacco (Nicotiana tabacum) in comparison to EDTA, but no toxicity to microorganisms. The uptake of Cu was increased by the addition of EDTA and EDDS, while no increase was observed in the uptake of Cd. Both chelating agents showed a very low root to shoot translocation capability and the translocation factor was lower than the one of the control. Heavy metals where significantly more phytoavailable than in the control, even after harvesting, resulting in a high heavy metal leaching possibility, probably owing to a low biodegradation rate of EDDS. New seedlings which were transplanted into the EDDS treated pots 7d after the phytoextraction experiment, showed signs of necrosis and chlorosis, which resulted in a significantly lower biomass in comparison to the control. The seedlings on the EDTA treated pots showed no toxicity signs. Contrary to previous opinions the results of this study revealed the chelating agents EDTA and EDDS as unsuitable for enhanced phytoextraction using tobacco.     

Mixing-controlled biodegradation in a toluene plume--results from two-dimensional laboratory experiments

Various abiotic and biotic processes such as sorption, dilution, and degradation are known to affect the fate of organic contaminants, such as petroleum hydrocarbons in saturated porous media. Reactive transport modeling of such plumes indicates that the biodegradation of organic pollutants is, in many cases, controlled by mixing and therefore occurs locally at the plume's fringes, where electron donors and electron-acceptors mix. Herein, we aim to test whether this hypothesis can be verified by experimental results obtained from aerobic and anaerobic degradation experiments in two-dimensional sediment microcosms. Toluene was selected as a model compound for oxidizable contaminants. The two-dimensional microcosm was filled with quartz sand and operated under controlled flow conditions simulating a contaminant plume in otherwise uncontaminated groundwater. Aerobic degradation of toluene by Pseudomonas putida mt-2 reduced a continuous 8.7 mg L(-1) toluene concentration by 35% over a transport distance of 78 cm in 15.5 h. In comparison, under similar conditions Aromatoleum aromaticum strain EbN1 degraded 98% of the toluene infiltrated using nitrate (68.5+/-6.2 mg L(-1)) as electron acceptor. A major part of the biodegradation activity was located at the plume fringes and the slope of the electron-acceptor gradient was steeper during periods of active biodegradation. The distribution of toluene and the significant overlap of nitrate at the plume's fringe indicate that biokinetic and/or microscale transport processes may constitute additional limiting factors. Experimental data is corroborated with results from a reactive transport model using double Monod kinetics. The outcome of the study shows that in order to simulate degradation in contaminant plumes, detailed data sets are required to test the applicability of models. These will have to deal with the incorporation of existing parameters coding for substrate conversion kinetics and microbial growth.     

Mitigation Costs in a Globalized World: Climate Policy Analysis with REMIND-R

Within this paper, we present the novel hybrid model REMIND-R and its application in a climate policy context based on the EU target to avoid a warming of the Earth’s atmosphere by more than 2°C compared to the pre-industrial level. This paper aims to identify necessary long-term changes in the energy system and the magnitude of costs to attain such a climate protection target under different designs of the post-2012 climate policy regime. The regional specification of mitigation costs is analyzed in the context of globalization where regions are linked by global markets for emission permits, goods, and several resources. From simulation experiments with REMIND-R, it turns out that quite different strategies of restructuring the energy system are pursued by the regions. Furthermore, it is demonstrated that the variance of mitigation costs is higher across regions than across policy regimes. First-order impacts, in particular, reduced rents from trade in fossil resources, prevail regardless of the design of the policy regime.     

Characterisation of PM10 emissions from woodstove combustion of common woods grown in Portugal

A series of source tests was performed to evaluate the chemical composition of particle emissions from the woodstove combustion of four prevalent Portuguese species of woods: Pinus pinaster (maritime pine), Eucalyptus globulus (eucalyptus), Quercus suber (cork oak) and Acacia longifolia (golden wattle). Analyses included water-soluble ions, metals, radionuclides, organic and elemental carbon (OC and EC), humic-like substances (HULIS), cellulose and approximately l80 organic compounds. Particle (PM₁₀) emission factors from eucalyptus and oak were higher than those from pine and acacia. The carbonaceous matter represented 44–63% of the particulate mass emitted during the combustion process, regardless of species burned. The major organic components of smoke particles, for all the wood species studied, with the exception of the golden wattle (0.07–1.9% w/w), were anhydrosugars (0.2–17% w/w). Conflicting with what was expected, only small amounts of cellulose were found in wood smoke. As for HULIS, average particle mass concentrations ranged from 1.5% to 3.0%. The golden wattle wood smoke presented much higher concentrations of ions and metal species than the emissions from the other wood types. The results of the analysis of radionuclides revealed that the ²²⁶Ra was the naturally occurring radionuclide more enriched in PM₁₀. The chromatographically resolved organics included n-alkanes, n-alkenes, PAH, oxygenated PAH, n-alkanals, ketones, n-alkanols, terpenoids, triterpenoids, phenolic compounds, phytosterols, alcohols, n-alkanoic acids, n-di-acids, unsaturated acids and alkyl ester acids.     

Teleconnections,midlatitude cyclones and Aegean Sea turbulent heat flux variability on daily through decadal time scales

We analyze daily wintertime cyclone variability in the central and eastern Mediterranean during 1958–2001 and identify four distinct “cyclone states,” corresponding to the presence or absence of cyclones in each basin. Each cyclone state is associated with wind flows that induce characteristic patterns of cooling via turbulent (sensible and latent) heat fluxes in the eastern Mediterranean basin and Aegean Sea. The relative frequency of occurrence of each state determines the heat loss from the Aegean Sea during that winter, with largest heat losses occurring when there is a storm in the eastern but not central Mediterranean (eNOTc) and the smallest occurring when there is a storm in the central but not eastern Mediterranean (cNOTe). Time series of daily cyclone states for each winter allow us to infer Aegean Sea cooling for winters prior to 1985, the earliest year for which we have daily heat flux observations. We show that cyclone states conducive to Aegean Sea convection occurred in 1991/1992 and 1992/1993, the winters during which deepwater formation was observed in the Aegean Sea, and also during the mid-1970s and the winters of 1963/1964 and 1968/1969. We find that the eNOTc cyclone state is anticorrelated with the North Atlantic Oscillation (NAO) prior to 1977/1978. After 1977/1978, the cNOTe state is anticorrelated with both the NAO and the North Caspian Pattern, showing that the area of influence of large-scale atmospheric teleconnections on regional cyclone activity shifted from the eastern to the central Mediterranean during the late 1970s. A trend toward more frequent occurrence of the positive phase of the NAO produced less frequent cNOTe states since the late 1970s, increasing the number of days with strong cooling of the Aegean Sea surface waters.